Alkaloids Solanum

Thirty two Solanum species have been investigated for their 

The maximum solasodine content of both berries and leaves in this 2 2 

The glycoalkaloid content of sixteen wild, tuber-bearing Solanum species has been investigated the solasodine glycosides sola- 

Solamargine and solasonine have been isolated from berries of 

The same glycoalkaloids, together with solanine, were detected in 

The known glycoalkaloids, their corresponding alkamines, and their sugar moiety are given in Table 1. 

Alkaloid from S. Aglycone C27H43O2N L-Rhamnosido-D-galacto- 

CsoHgjOjiN C27H45O2N D-xylose, 1 mole D-galactose and 2 moles D-glucose 

The two most widely distributed glycoalkaloids, solanine and solason-ine, as well as the less-known solauricine and the alkaloid from Solanum panduraeforme Drege contain as sugar component a trisaccharide, L-rhamnosido-D-galactosido-D-glucose (I), for which the name solanose has been proposed (11, 12, 13, 14, 38, 60, 62). 

The recently isolated solasodamine contains as sugar compound a tetrasaccharide consisting of two moles of L-rhamnose and one each of D-galactose and D-glucose, probably represented by II (12). A trisaccharide not identical with solanose has been obtained from solamargine. 

The solanum alkaloids occurring in species of Solarium, including potatoes, Dead Sea Apple, and poro-poro, also contain the steroid nucleus 

Dihydrosolagenin (demissidin), combined with a tetrasaccharide, was found in Solarium demissum 29). This tetrasaccharide, also found in tomatin, the glycosidic alkaloid of tomato plants, is a xylosyl-glucosyl-glucosyl-galactose 30). 

Plants containing demissin are not affected by the larva of the potato beetle 29). This doubtlessly arises from the presence of the alkaloid, since, normally, potato leaves are avoided when they have a gelatinous layer containing demissin. Crossbreeding between species containing solanin and demissin does not lead to the expected resistance, because the demissin content decreases in the hybridization 31). 

The Solanum steroidal alkaloids10 and the distribution of alkaloids in Australian Solanum species11 have been reviewed. A review on the constituents of tomatoes includes discussion on the tomato glyco-alkaloids.12 

The aglycon solasodine (8) is becoming increasingly important as a starting material for the synthesis of steroids in the pharmaceutical industry,13 and aspects of the isolation and chemistry of solasodine have been reviewed in this light.14 

Terada and H. Mitsuhashi, Chem. Pharm. Bull., 1979, 27, 2304 (Chem. Abstr., 1980,92, 72 674) S. Terada, K. Hayashi, and H. Mitsuhashi, Tennen Yuki Kagobutsu Toronkai Koen Yoshishu, 21st, 

A O-Diacetyldihydropseudosolasodine (12a) gave the epimeric pyrrolidines (13) on treatment with bromine. When N-bromosuccinimide was used as oxidant, the ketone (12b) and the pyrrolidine (14) were also formed.17 The WolfF-Kishner reductions of solasodenone (9b) and of the epimeric 4,5 -dihydro-analogues have been reported.18 Solasodine gave the expected 5a,6-epoxide on treatment with perbenzoic acid.19 The preparation of an intermediate in the synthesis of the solanidine alkaloids has been reviewed.20 

Solasodine (0.01%), tomatidenol (0.001%), and a new Solarium alkaloid, solanaviol (0.05%), have been isolated from dried leaves of S. aviculare.21 Solanaviol was assigned the structure 12/3-hydroxysolasodine (15a) on the basis of mass-spectral and H and 13C n.m.r. studies and the conversion of solanaviol 

The mass spectra of. Solanum bases have been reviewed (J. Tamas and M. Mak, Chem. Abs., 1977, 87, 102514 1983, 198590). Complete assignments for -nmr resonances of a number of Solanwn alkaloids have been published (G. J. Bird etal.. Austral. J. Chem., 1979, 783, 797). H.p.l.c. 

Solasodenone (24) has been oxidized with potassium permanganate-sodium periodate to yield the keto-acid (25). The same starting material gave (26) on Wollf-Kishner reduction of the ketone moiety followed by treatment of the product with lithium aluminium hydride the corresponding 4,5a- and 4,5/3-dihydro-derivatives of (26) were similarly prepared.  

Two novel, isomeric, 3-amino-20-pyridyl-pregnanes (C27H42N2O2) have been isolated from Solarium seaforthianum and named solaseaforthine (29a) and 

The structure (34a) of 25-isosolafloridine, isolated from S. callium, was earlier assigned in part by an X-ray crystallographic study,while that of the accompanying base solacallinidine (34b) was deduced on the basis of spectroscopic comparison with the former alkaloid. A chemical correlation of the two alkaloids, together with details of their isolation and structure determination, have now been published. Details of the isolation from S. dunalianum and the structure determination of soladunalinidine (35a) have appeared tomatidine (3Sb) was also isolated from the same plant. Solafilidine (36a) and desacetyl-solafilidine (36b) have been isolated in high yield from dried fruits of S. affin. ecuadorensis.  

A comprehensive survey of the solasodine content of 85 native Australian Solanum species has been published. Several studies have appeared which describe the changes in distribution and concentration of solasodine during the Ufe cycle of S. laciniatum. The effects of light colour on the solasodine content of 5. laciniatum and on the solasodine content of clones of 5. dulcamara have been studied the effect of ecological factors on alkaloid production by these two species has also been investigated. The solasodine contents of developing berries,fruits, and seed callus of S. khasianum have been reported. 

Ivanchenko and E. A. Tukalo, Fitokhim. Izuch. Flory B. SSR, Biofarm. Issled. Lek. Prep., 1975, 97 [ed. E. N. Medvedskii, Leningrad Med. Inst, im I. P. Pavlova Leningrad, USSR] (Chem. Abs., 1978,89,3153). 

---

The structural features of the solanum alkaloids are based on two primary skeletal configurations solanidane, with or without glycoside functionalities, as featured by the toxic and teratogenic steroidal alkaloids a-chaconine and a-solanine with the indolizidine type E-F ring (Figure 2.7a) and the spirosolane... 

Kusano, G., Takahashi, A., Nozoe, S., Sonoda, Y. and Sato, Y. 1987. Solanum alkaloids as inhibitors of enzymatic conversion of dihydrolanosterol into cholesterol. Chemistry and Pharmacy Bulletin, 35 4321 323. 

Sohreiber, K. 1963. On the appearance of glycoside alkaloid in tuber-bearing species of the genus Solanum L. solanum alkaloids. XXVII. KulturpHanze 11 422-450. 

Chromatographic analysis of glycoalkaloids can be performed in a number of ways (321,322). The intact compounds can be analyzed by GC after derivatization (323). After hydrolysis the aglycone skeleton can be examined by GC without the need of derivatization (324). For routine determinations of the glycoalkaloids present in potato tubers, HPLC is probably the method of choice. Column acidity caused by active silanol sites on the packing surface strongly influences the chromatographic separation of Solanum alkaloids. In fact, basic compounds react with... 

Schreiber, K., Aurich, O., and Osske, G., Solanum alkaloids. XVBI. Thin-layer chromatography of Solanum steroid alkaloids and steroidal sapogenins, J. Chromatogr., 12, 63, 1963 Chem. Abs., 60, 4442h, 1964. 

Syntheses have been reported of three analogues (45),32 (46),33 and (47)34 of naturally occurring Solanum alkaloids. 

The family Solanaceae is one of the important and interesting plant families. It may be classified into four groups based on their usefulness and chemical composition of alkaloids contained (1) Nicotiana spp. such as N. tabacum and N. rustica, which provide tobacco and contain nicotiana alkaloids such as nicotine and nomicotine (2) Hyoscyamus, Scopolia, Atropa, and Datura species, which are pharmacologically important and contain tropane alkaloids such as hyocyamine, scopolamine, and tropine (3) Solanum spp., which are sometimes the starting material for production of synthetic steroids for medical uses and which contain solanum alkaloids and (4) Capsicum, Solanum, and Lycoper-sicum species, which serve as foods and are alkaloid-free. 

Solasodine (1) and related Solanum alkaloids are useful starting materials for the commercial preparation of steroid hormones." In particular the pregnane derivative (6) was prepared from solasodine in 65% overall yield via the intermediates (2), (3), and (4). The oxidative cleavage of the 20(22) double bond of pseudosolasodine diacetate (3), which is the least efficient step in this synthesis, has been investigated in more detail With sodium dichromate in acetic acid compound (3) gave the hydroxyester (5) and the hydroxylactone (7), in addition to the ester (4). Results of a kinetic study of this reaction were interpreted in terms of formation of hydroxyester (5) via allylic oxidation of pseudosolasodine diacetate prior to cleavage of the 20(22) double bond. ... 

The solanum alkaloids solafloridine (431a) and 25-iso-solafloridine (432) have been prepared by a multi-step synthesis from 3)8,16a-diacetoxy-20-(5-methyl-2-pyridyl)pregna-5,20-diene (428). The pyridine ring of compound... 

L. H. Briggs and L. C. Vining, Solanum alkaloids. X. Mode of linkage in trisaccharide moiety of solanine and solasonine, J. Chem. Soc., (1953) 2809-2815. 

---